N-trityl-imidazolium salt

ABSTRACT

N-TRITYL-IMIDAZOLIUM SALTS OF THE FORMULA:   (1-(DI(PHENYL-)(R-PHENYL)C-)IMIDAZOLIUM) Y(-)   WHEREIN R IS HYDROGEN OR HALO AND Y IS THE ANION OF AN INORGANIC OR ORGANIC ACID AND ARE USEFUL AGAINST FUNGI PATHOGENIC TO PLANTS.

United States Patent US. Cl. 260-309 1 Claim ABSTRACT OF THE DISCLOSUREN-trityl-imidazolium salts of the formula:

(HEP- aHs wherein R is hydrogen or halo and Y is the anion of aninorganic or organic acid and are useful against fungi pathogenic toplants.

This is a divisional of our co-pending application Ser. No. 789,602,filed Jan. 7, 1969, now abandoned.

The present invention relates to and has for its objects the provisionfor particular new N-trityl-imidazolium salts of inorganic and organicacids, i.e. N-triphenylmethyland 1[(halophenyl)-(bisphenyl)-methyl]-imidazolium salts of inorganic andorganic acids, which possess fungicidal properties, active compositionsin the form of mixtures of such compounds with solid and liquiddispersible carrier vehicles, and methods for producing such compoundsand for using such compounds in a new way especially for combatingfungi, with other and further objects becoming apparent from a study ofthe within specification and accompanying examples.

It is already known that certain N-trityl-imidazoles exhibit fungicidalproperties (compare US. Pat. 3,321,366).

It has been found in accordance with the present invention, that theparticular new N-trityl-imidazolium salts of the formula exhibit strongfungicidal properties.

In our copending US. application, Ser. No. 789,601, filed Jan. 7, 1969,now abandoned, N-trityl-imidazoles, rather than N-trityl-imidazoliumsalts of the instant type, are disclosed and claimed which also possesssuperior fungicidal properties.

The invention also provides a process for the produc- 3,711,502 PatentedJan. 16., 1973 tion of such new N-trityl-imidazolium salts of Formula Iabove in which a trityl-imidazole of the formula 10 in which R is thesame as defined above, is reacted with an inorganic or an organicacid(IIb).

It is very surprising that the N-trityl-imidazolium salts of the presentinvention exhibit a considerably greater fungicidal activity thanpreviously known tritylimidazoles.

The instant active compounds therefore represent a valuable enrichmentof the art.

The production reaction according to the present invention isillustrated by the followng typical equation:

Advantageously, in accordance with the present invention, in the variousformulae set forth herein:

R represents hydrogen, or halo such as chloro, fluoro, bromo and iodo,including ortho, meta and para halo, especially ortho, meta and parachloro and fluoro; and Y is the anion of an:

inorganic acid, i.e. mineral acid, such as a hydrohalide includinghydrochloric, hydrofluoric, hydrobromic and hydroiodic; sulfuric acid;orthophosphoric acid; nitric acid; and the like, especially monoandpoly-basic inorganic acids, such as monoto tri-basic inorganic acids,preferably halides and particularly chloride; or organic acid includingaliphatic carboxylic acids, e.g. lower aliphatic hydrocarbon carboxylicacid, especially having 2-8 carbon atoms, such as monoandpoly-carboxylic, including monoto tri-carboxylic, saturated andunsaturated, e.g. monoand diethylenically unsaturated, optionallymonoand poly-, especially monoto tri-, hydroxy-substituted, acids;including lower alkanoic, especially C or C alkanoic, acids such asacetic, propionic,

butyric, pentanoic, hexanoic, heptanoic,

octanoic, and the like, acids; lower alkanedioic, especially C or Calkanedioic, acids, such as malonic [HO0CCH COOH] succinic [HOOC-(CH-COOH], glutaric [HOOC-(CH -COOH], adipic [H0OC(CH C0OH], pimelic[HOOC(CH COOH] suberic [HOOO(CH -COOH], and

like, acids; lower alkanetricarboxylic acids, especially C or Calkanetricarboxylic, acids such as tricarballylic (HOOC-CHz) --CH--COOH]and the like, acids;

lower alkenoic, especially C or C alkenoic, acids such as acryliccrotonic [CH -CH==CH-COOH], methacrylic [CH =(J(CH )-COOH], vinylacetic[CI-IFCHCH COOH], pent- -2-, -3- and -4- -enoic, hex- -2-, -3-, -4- and-5- -enoic, pyroterebic and the like, acids; lower alkadienoic,especially C 01' C alkadienoic, acids such as sorbic [CH (CH=CH-) COOH]and the like, acids;

lower alkenedioic, especially C or C alkenedioic, acids such as maleic[cis HOOC-CH -CH-COOH] fumaric [trans HOOC--CH=CHCOOH] citraconic[HOOCC(CH )=CHCOOH] allylmalonic and the like, acids; loweralkadienedioic, especially C or C 4 al-kadinedioic, acids such asmuconic and the like, acids; and

hydroXy-substituted lower, e.g. C or C or- C alkanoic,hydroxy-substituted lower, e.g. C or C alkanedioic, andhydroxy-substituted lower, e.g. C or C alkanetricarboxylic, acids suchas glycollic [HOCH -COOH], lactic malic [HOOCCH CH(OH)COOH] tartaric[HO0C:- CH(OH)-CH(OH)COOH] citric [HOOC--CH --C(0H) and the like, acids,especially monoto trihydroxy alkan monoto tri-oic acid; and aromaticmonoand poly-canboxylic acids including C aryl hydrocarbon carboxylicacids, e.=g. aromatic or C aryl monoto tricarboxylic acids, optionallymonoand poly-, e.g. monoto tri-, hydroxy substituted, especially benzenemonoand poly-, e.g. monoto tri-, carboxylic acids, optionally monoandpoly-, e.g. monoto tri-, hydroxy substituted, including benzenemonocarboxylic acid, i.e. benzoic acid; benzene dicarboxylic acids, suchas phthalic, isophthalic and terephthalic acids, i.e. ortho, meta andpara dicarboxyl benzene; benzene tricarboxylic acids such ashemimellitic, mellitic and trimesic acids,-i.e. 1,2,3-, 1,2,4- and1,3,5-tricarboxyl benzene; and the like, monohydroxy-benzenemonocarboxylic acids such as salicylic acid, i.e. orthohydroxybenzenemonocarboxylic acid, as well as as meta and para hydroxy-benzenemonocarboxylic acid, and the like;

dihydroxy benzene monocarboxylic acids such as S-hydroxyl salicylic acid(gentistic acid), i.e. 2,5-dihydroxy-benzoic acid, resorcylic acid, i.e.3,5-, 2,4- and 2,6-dihydroxy-benzoic acid, and the like;

trihydroxy benzene monocarboxylic acids such as pryogallol carboxylicacid, i.e. 2, 3,4-trihydroxy benzoic acid, and the like;

monohydroxy benzene dicarboxylic acids such as hydroxy phthalic,isophthalic and terephthalic acids, i.e. 4-hydroxy-1,2-dicarboxylbenzene, 3-hydroxy-l,2-dicarboxyl benzene, 2-hydroxy-1,3 dicarboxylbenzene, 4-hydroXy-1,3-dicarboxyl benzene, 5- hydroxy-l,3-dicarboxybenzene, 2-hydroxyl,4*dicarboxyl benzene, and the like;

dihydroxy-benzene dicarboxylic acids such as 3,4- and3,5-dihydroxy-1,2-dicarboxyl benzene, 2,4- and2,5-dihydroxy-1,3-dicarboxyl benzene, 2,3- and2,5-dihydroXy-1,4-dicarboxyl benzene, and the like;

trihydroXy-benzene dicarboxylic acids such as3,4,5-trihydroxy-l,Z-dicarboxylbenzene, 2, 4,5-trihydroxy-1,3-dicarboxylbenzene, 2,3, S-trihydroxy-1,4-dicarboxyl benzene and the like;

monohydroxy-benzene tricarboxylic acids such as 4- andS-hydroxy-1,2,3-tricarboxyl benzene, 3- and 5-hydroXy-l,2,4-tricarboxylbenzene, 2-hydroxy-1,3,5-tricarboxyl benzene, and the like;

dihydroxy-benzene tricarboxylic acids such as 4,5-dihydroxy1,2,3-tricarboxyl benzene, 3,6-dihydroxy 1,2,4-tricarboxyl benzene,2,4-dihydroxy 1,3,5-tricarboxyl benzene, and the like; and

trihydroxy-benzene tricarboxylic acids such as4,5,6-trihydroxy-1,2,3-tricarboxyl benzene, 3,5,6-trihydroxy1,2,4-tricarboxyl benzene, 2,4,6-trihydroxy-1,3,5-tricarb0xyl benzene,and the like.

Preferably, R is hydrogen or halo, especially chloro or fiuoro; and Y isthe halo anion, especially chloro; or the anion of C or C alkanoic acid,especially acetic acid; or C or C alkanedioic acid, especiallymonosuccinic acid; or C or C alkanedioic acid, especially mono-maleicacid; or C or C alkedienoic acid, especially sorbic acid; or hydroxy-Cor C alkanoic acid, especially lactic acid; or hydr0Xy-C or Calkanetricarboxylic acid, especially mono-citric acid; or dihydroxy-C orC alkanedioic acid, especially tartaric acid; and the like.

In particular, where R is halo, especially chloro o-r fluoro, Y is thechloro anion or the anion of an hydrogry-C L alkanoic acid, especiallythe anion of lactic aci The N-trityl-imidazoles useable as startingmaterials are clearly characterized by the Formula IIa above.

Some of the trityl-imidazole starting materials are known, for exampletrityl-imidazole and 1-[(p-chlorophenyl)-(bisphenyl)-methyl]-imidazole.Those which are new can be prepared in the same manner as those whichare known.

The starting N-trityl-imidazoles of the Formula I'Ia are obtained inparticularly favorable manner when the appropriate startingtrityl-halide is reacted .With imidazole in a polar inert organicsolvent, such as acetonitrile, dimethyl formamide or nitromethane, at atemperature of from 0 to C. in the presence of an acid binder, such astriethylamine or pyridine.

Trityl chloride is already known. Some of the monosubstituted startingtritylhalides are known, ThQSQ t r tritylhalides which are new can beprepared in the same manner as the known ones.

The preparation of the mono-substituted trityl chlorides may be carriedout as follows:

The Grignard compound of the mono-substituted benzene is prepared. Thephenylmagnesium bromide so obtained is then reacted with benzophenone.The organornetallic complex compound obtained is subjected tohydrolysis, the appropriate alcohol being formed (compare J. Org. Chem.7, 392 (1942)).

The chloride may be easily prepared from the alcohol, when the alcoholis reacted with anhydrous hydrogen chloride or with thionyl chloride.The hydroxyl group is replaced by chlorine (compare J. Org. Chem. 7, 392(1942) The acids usable as starting materials for the process accordingto the invention are of course also known and include inorganicmonobasic or polybasic acids, or organic aliphatic monoorpoly-carboxylic acids which may be saturated or unsaturated, or aromaticmonoor polycarboxylic acids. These organic acids may be substituted,preferably by one or more hydroxyl groups.

It is preferable to use acids which are not phytotoxic. As is known,some very specific organic acids have a phytotoxic activity. Theseinclude the substituted phenoxyacetic acids, phenoxypropionic acids andphenoxy- 'butyric acids, such as 2,4-dichlorophenoxy-acetic acid and2-methyl-4-chloro-phenoxy-propionic acid.

Particularly suitable acids, for example, include: hydrochloric acid,hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, aceticacid, glycollic acid, lactic acid, malonic acid, succinic acid, glutaricacid, adipic acid, sorbic acid, pyroterebic acid, fumaric acid, maleicacid, citric acid, citraconic acid, tartaric acid, malic acid, muconicacid, allylmalonic acid, benzoic acid, salicylic acid, and the like.

The production reaction according to the present invention may becarried out in the presence of solvents, which term includes merediluents.

These solvents and diluents include especially the chlorinatedhydrocarbons, such as chlorobenzene and carbon tetrachloride; ethers,such as diethyl ether, dioxan and tetrahydrofuran; nitriles, such asacetonitrile; amides, such as dimethyl formamide; and sulfoxides, suchas dimethyl sulfoxide; and the like. It is expedient to use stronglypolar solvents which dissolve both reaction components as completely aspossible. Aqueous diluents are less suitable since losses may occurbecause ofhydrolytic splitting up of the N-trityl compound.

The reaction temperatures which may be used can be varied within afairly wide range. In general, the reaction is carried out atsubstantially between about 10 to 60 C., preferably between about to 50C.

When carrying out the reaction, about one mol of acid is normally usedfor each mol of imidazole, i.e. whereby to form the equivalent salt. Thereactants are suitably mixed in a solvent which, after the reaction, isevaporated oif wholly or in part. It is often expedient to add ether topromote crystallization.

Advantageously, the particular new active compounds of the presentinvention exhibit a strong fungitoxic ac tivity. Because of their lowtoxicity to warm-blooded animals the instant compounds are suitable forthe control of undesired fungus growth. Their good compatibility withhigher plants permits the instant compounds to be used as plantprotection agents against fungal plant diseases.

The instant active compounds are particularly suitable for the controlof phytopathogenic fungi on above-thesoil parts of plants as well asagainst phytopathogenic fungi which attack the plants from the soil.

The instant active compounds exhibit a particularly high fungicidalpotency against powdery mildew fungi from the family of theErysiphaceae, for example against the fungi of the genera Erysiphe,Oidium and Podoshaera; and the like. The instant active compounds can,however, also be used with good results for the control of otherphytopathogenic fungi, for example fungi which cause diseases in riceand ornamental plants. The instant active compounds shOW a good activityagainst Piricularia oryzae, Pllicularia sasakii and Cochliobolusmiyabeanus, three pathogenic agents which occur in rice; and againstCercospora musae; and the like. Furthermore, the growth of Phialosphoracinerescens, a fungus which attacks carnations from the soil, is alsoinhibited.

The instant active compounds are distinguished by a high effectivenessin very low concentrations and by a good compatibility with plants. Forthis reason, dosages higher than necessary for the fungicidal effect canbe accepted readily by such plants.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withinert conventional pesticidal diluents or extenders, i.e. inertconventional pesticidal dispersible carrier vehicles, such as solutions,emulsions, suspensions, emulsifiable concentrates, spray powders,pastes, soluble powders, dusting agents, granules, etc. These areprepared in known manner, for instance by extending the active compoundswith conventional pesticidal dispersible liquid diluent carriers and/ordispersible solid carriers, optionally with the use of carrier vehicleassistants, e.g. conventional pesticidal urface-active agents, includingemulsifying agents and/or dispersing agents, whereby, for example, inthe case where water is used as diluent, organic solvents may be addedas auxiliary solvents. The following may be chiefly considered for useas conventional carrier vehicles for this purpose: inert dispersibleliquid diluent carriers including inert organic solvents, such asaromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.),halogenated, especially chlorinated, aromatic hydrocarbons (e.g.chlorobenzenes, etc.), paraffins (e.g. petroleum fractions), chlorinatedaliphatic hydrocarbons (e.g. methylene chloride, etc.), alcohols (e.g.methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolarnine,etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.),amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethylsulfoxide, etc.), ketones (e.g. acetone, etc.), and/or water; as well asinert dispersible finely divided solid carriers, such as ground naturalminerals (e.g. kaolins, alumina, silica, chalk, i.e. calcium carbonate,talc, kieselguhr, etc.) and ground synthetic minerals (e.g. highlydispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereasthe following may be chiefly considered for use as conventional carriervehicle assistants, e.g. surface-active agents, for this purpose:emulsifying agents, such as nonionic and/or anionic emulsifying agents(e.g. polyethylene oxide esters of fatty acids, polyethylene oxideethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., andespecially alkyl aryl-polygylcol ethers, magnesium stearate, sodiumoleate, etc.); and/or dispersing agents, such as lignin, sulfite wasteliquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/ or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other fungicides, orherbicides, insecticides, bactericides, etc., if desired, or in the formof particular dosage preparations for specific application madetherefrom, such as solutions, emulsions, suspension, powders, pastes,and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 01-95%, and preferably0.5- by weight of the mixture, Where as carrier composition mixturessuitable for direct application or field application generallycontemplate those in which the active compound is present in an amountsubstantially between about 0.00001-2%, preferably 0.0001-1%, by weightof the mixture. Thus, the present invention contemplates over-allcompositions which comprise mixtures of a conventional dispersiblecarrier vehicle such as (1) a dispersible carrier solid, and/or (2) adispersible carrier liquid such as an inert organic solvent and/or waterpreferably including a surface-active effective amount of a carriervehicle assistant, e.g. a surface-active agent, such as an emulsifyingagent and/ or a dispersing agent, and an amount of the active compoundwhich is effective for the purpose in question and which is generallyabout 000001- 95%, and preferably 0.000195%, by weight of the mixture.

The active compound can also be used in accordance with the Well-knownultra-low-volume process with gOOd success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment in finelydivided form, e.g. average particle diameter of from 50-100 microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 1 quart/acre, preferably 2-16 fluidounces/ acre, are sufiicient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing -80%, preferably 20-60%, or generally from about 20to about 95% by weight of the active compound, or even the 100% activesubstance alone, e.g. about 10-100% by Weight of the active compound.

In particular, the present invention contemplates methods of selectivelykilling, combating or controlling fungi, which comprises applying to atleast one of (a) such fungi and (b) their habitat, i.e. the locus to beprotected, a fungicidally effective or toxic amount of the particularactive compound of the invention alone or together with a carriervehicle as noted above. The instant formulations. or compositions areapplied in the usual manner, for instance by spraying, atomizing,vaporizing, scattering, dusting, watering, sprinkling, pouring, and thelike.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases, it ispossible to go above or below the aforementioned concentration ranges.

The fungicidal effectiveness of the new compounds of the presentinvention is illustrated, without limitation, by the following examples.

EXAMPLE 1 Podosphaera test (powdery mildew of apples) [Protective]Solvent: 4.7 parts by weight acetone Emulsifier: 0.3 part by weightalkylaryl polyglycol ether Water: 95.0 part by weight The amount of theparticular active compound required for the desired concentration ofsuch active compound in the spray liquid is mixed with the stated amountof solvent, and the resulting concentrate is diluted with the statedamount of water which contains the stated emulsifier.

Young apple seedlings in the 4-6 leaf stage are sprayed (treated) withthe active compound spray liquid until dripping wet. The plants remainin a greenhouse for 24 hours at 20 C. and at a relative atmospherichumidity of 70%. Such plants are then inoculated by dusting with conidiaof the apple powdery mildew causative organism (Podosphaera leucotrichaSalm.) and placed in a greenhouse at a temperature of 21-23" C. and at arelative atmospheric humidity of about 70%.

Ten days after the inoculation, the infestation of the seedlings isdetermined as a percentage of the untreated but also inoculated controlplants.

0% means no infestation, and means that the infestation is exactly asgreat as in the case of the control plants.

The particular active compounds tested, their concentrations and theresults obtained can be seen from the following Table 1.

TABLE I.PODOSPHAERA TEST (PROTECTIVE) Infestation as a percentage of theinfestation of the untreated control with a concentration of activecompound (in percent) of- Active compound 0. 00156 Known:

Active compounds according to the invention: corresponding to Formula Iin which R is H and Y has the following meaning, respectively:

OH CHaH-(JO O (8 OHa 36 H=CH-C O 9 EXAMPLE 2 Example 1 was repeatedusing the compounds and obtaining the results given in Table 2 below.

TABLE 2.PODOSPHAERA TEST (PROTECTIVE) Infestation as a percentage of theinfestation of the untreated control with a concentration of activecompound (in percent) of- Active compound 0. 0031 0. 00156 Activecompound corresponding to Formula I in which R and Y have the followingmeaning, respectively:

(121) (3H3 m-F 5 16 CHOH JJ 059 (131) C1 p-F 18 15 (141) CH3 p-F 21 18(SHOE p-Cl 31 31 m-Cl 0 9 m-Ol 0 16 EXAMPLE 3 Erysiphe test Solvent: 4.7parts by weight acetone Emulsifier: 0.3 part by weight alkylarylpolyglycol ether Water: 95.0 parts by weight The amount of theparticular active compound required for the desired concentration in thespray liquid is mixed with the stated amount of the solvent, and theresulting concentrate is diluted with the stated amount of watercontaining the stated emulsifier.

Young cucumber plants (Delikatess variety) with about three foliageleaves are sprayed (treated) with the active compound spray liquid untildrip-ping wet. The cucumber plants remain in a greenhouse for 24 hoursto dry. Such plants are then, for the purpose of inoculation, dustedwith conidia of the fungus Erysiphe polyphaga. The plants aresubsequently placed in a greenhouse at 2324 C. and at a relativeatmospheric humidity of about 75% After 12 days, the infestation of thecucumber plants is determined as a percentage of the untreated but alsoinoculated control plants. 0% means no infestation, and 100% means thatthe infestation is exactly as great as in the case of the controlplants.

The particular active compounds tested, their concentrations and theresults obtained can be seen from the following Table 3.

TABLE 3.ERYSIPHE TEST Infestation as a percentage of the infestation ofthe untreated control with a concentration of active compound (inpercent) of Active compound 0,0001!) Known Active compounds according tothe invention: corresponding to Formula I in which R is H and Y has thefollowinlz meaning, respectively:

CH1 (HO O O 9 (31) C O OH 10 BE OH (5 O O 9 (42) C O O 9 10 H O H I H011C 0 O H (5 CHz-C 02H 10 2) c a a 20 (82) CH: trans 3 H II (311 CH=CH-C0:

1 1 EXAMPLE 4 Example 3 was repeated using the compounds and ob- 12EXAMPLE Mycelium growth test taining the results given in Table 4 below:Nutrient medium used:

5 Parts by wt. Agar-agar 20 TABLE 4.ERYSIPHE TEST f i extract 30Distilled water 950 Infestation as a perg f fj Proportion of solvent tonutrient medium:

' reassure Parts by active compound (in Acetone 2 Active compoundpercent) of 0.00019 Agar nutrient medium 100 gg gt gi gfg f gfggfgg gfig The amount of the particular active compound required Yhavethejollowing meanfor the desired concentration of such active compoundmg'respecmely' in the nutrient medium is mixed with the stated amount YR of solvent. The resulting concentrate is thoroughly mixed, (m) CH 0 inthe stated proportion, with the liquid nutrient medium j (which has beencooled to 42 C.) and is then poured into HOH Petri dishes of 9 cm.diameter. Control dishes to which 0, the active compound preparation hasnot been added are 12, CH m-F 7 also set P- t When the nutrient mediumhas cooled and solidified, HOE the dishes are inoculated with thespecies of fungi stated 01 in the table below and incubated at about 21C. (142) 0Hx 10 Evaluation is carried out after 4-10 days, dependent 1 Hupon the speed of growth of the fungi. When evaluation is HO carried outthe radial growth of the mycelium on the 02 treated nutrient media iscompared with the growth on the (162) P431 20 control nutrient media. Inthe evaluation of the fungus HOH growth, the following characteristicvalues are used: o e 0 no fungus growth 1 1 very strong inhibition ofgrowth 7:) 019 m- 2 medium inhibition of growth (18,) 1 .01 0 3 slightinhibition of growth J 0H 4 growth equal to that of untreated control.

029 The particularactive compounds tested, their concentrations and theresults obtained can be seen from the 40 following Table 5.

TABLE 5.MYCELIUM GROWTH TEST Fungi Concentration Philaoof activePirlcuphora Pelli- Cercos- Cochliocompound larz'a cinereculan'a parabusmiua Active compound in p.p.m. oryzae scene sasakii musae beanusKnown:

Active compounds according to the invention: corresponding to Formula Iin which R is H and Y has the following meaning, respectively: (14). (:110 0 o o 2 OHOH CHOH

COOH

TABLE -C0ntinued Concen- Fungi tration Philaoof active Pim'ew phomPell11- 0ercos- C'ochliocompound hmw cine'recularia pom bus miyo- Activecompound in p.p.m. ora/zae scans sasa-kii musae bcanus (51)- CHr-C 02H 0o 2 o 1 HO-CC 0,

0112-0 01H 6,)"; CHaC 0, 1o 0 0 a o 2 (7a)-.;': 10 0 o a 0 2 C On Theprocess for producing the particular new com- TABLEC011fi1111ed poundsof the present invention is illustrated, without MPq limitation, by thefollowing further examples: Y R

EXAMPLE 5 (74) H 160-168 N-triphenylmethyl-imidazolium lactate (2 31 g.N-trityl-imidazole are dissolved in acetonitrile by 0026 heating; 10 g.(0.11 mol) d, l-lactic acid are then added. 8 OH H 0 The residue afterthe solvent has been distilled 0E is made 3) a 15846 to crystallize bycovering with a layer of ether; the crys- I H talline product is washedwith ether and dried. (1H Yield: 40 g. of colorless crystalline powderof M.P. JH=CH-COn6 170-180 (93).; coin H 188-189 EXAMPLE 7 H,N-triphenylmethyl-imidazolium chloride (1 31 g. N-trityl-imidazole aredissolved in 400 ml. carbon 35 9 tetrachloride, and hydrogen chloride isthen introduced at (3 C 0 H H 200 206 room temperature. Thehydrochloride precipitates after 2 some time and is filtered ofl? withsuction. It is recrystal- H H (t lized from acetone/ether (1:1). CH tansYield: 33 g. of colorless crystals of M.P. 141 C. ,9

EXAMPLE 8 1- (p-chlorophenyl) (bisphenyl) -methyl] EXAMPLE 9 Thefollowing compounds were prepared in analogous manner.

imidazolium chloride (19 20 g. 1-[(p-chlorophenyD-(bisphenyl)-methyl]-imid- Y R M.P., o. azole aredissolved in 250 m1. carbon tetrachloride- Hy- 102 019 0-01 159 drogenchloride is introduced at room temperature until (m) CH: 120 about 1.5equivalents of hydrogen chloride are taken up. g} The hydrochlorideprecipitates and, after being left to E03 stand for two hours, isfiltered ofi with suction, Washed ,9 with carbon tetrachloride anddried. (123) CH3 11 0 Yield: 22 g. of colorless crystalline powder ofM.P. O 12s-130 c. 00,

In analogous manner, the following compounds accord- (132) C19 ing toFormula I are prepared: (14a) CH; p-F 95 HOE M.P., 039 Y R 0.

(152) p-F so (44) OH OH H 174480 HOzCH-(EHCO2 5,) CH C 01H H 138-145110-- co,e a) ?Ha p-0l 90 11100211 (IJHOH (6 onaool H 231 3 00 11 H 0-117 a) 1 mm 153-155 3 (55) 8a) H3 m-Cl 80-90 pJH HOH A! 02 PREPARATIONOF STARTING MATERIALS l-[ (p-chlorophenyl) -(bispheny1) -methyl]-imidazole (IIab) 13.6 g. (0.2 mol) imidazole are dissolved in 200 ml.of dry acetonitrile, and a solution of 31.4 g. -(0.1 mol)(p-chlorophenyl)-(bisphenyl)-methyl chloride in 50 ml. dimethylformamide is added. Heating at 80 C. is efiected for 3 hours, followedby clarification with activated charcoal, distillation of the solvent,and removal of the imidazole hydrochloride by digestion of the residuewith Water. After drying, recrystallization from light petroleum iseffected.

Yield: 31 g. of colorless crystalline powder of M.P. 139-140 C.

Preparation of I the (p chlorophenyl) (bisphenyl)- methyl chloriderequired as above starting material:

205 g. bromobenzene and 29 g. magnesium are reacted, in 1 liter of etherto give phenylmagnesium bromide and to this there are added dropwise 216g. of p-chlorobenzophenone dissolved in 1 liter of benzene, and stirringis elfected for 24 hours. Hydrolysis is then carried out with dilutehydrochloric acid, the solvent layer is taken OE, and drying anddistillation are then efiected. 306 g.(pchlorophenyl)-(bisphenyl)-carbino1 are obtained. This is taken up in 1liter of benzene, 50 g. calcium chloride are added and hydrogen chlorideis introduced into the solution until saturation. The oily productobtained after removal of the solvent crystallizes after some time. Byvigorous suction filtration, 220 g. (p-chlorophenyl)-bisphenyl)-methylchloride of M.P. 88 C. are obtained.

It will be realized by the artisan that all of the foregoing compoundscontemplated by the present invention possess the desired strongfungicidal properties, with regard to a broad spectrum of activity, asWell as a comparatively low toxicity toward warm-blooded creatures and aconcomitantly low phytotoxicity, enabling such compounds to be used Withcorrespondingly favorable compatibility with warm-blooded creatures andplants for more efiective control and/or elimination of fungi byapplication of such compounds to such fungi and/or their habitat.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:

1. N-trityl-imidazolium salt of the formula:

1 N I I l R 9 8 Y 3 0H5 wherein R is hydrogen and Y is H (Ijj' trans HoH=oHo02 References Cited UNITED STATES PATENTS 3,299,090 1/1967 Holt260309 3,321,366 5/1967 Mussell et a1 260-309 3,322,783 5/1967 Dunn260309.2 3,323,990 6/1967 Budde et a1 260309 3,418,318 12/1968 Lambie etal. 260309.2

OTHER REFERENCES Chemical Abstracts, The Naming and Indexing of ChemicalCompounds from Chemical Abstracts pages 26N32 N, Wash. DC, Amer. Chem.Soc., 1962.

Giesemann et al.: (1) Chem. Abstr. vol. 53, columns 10190-1 (1959).

Giesemann et al.: (II) Chem. Berichte vol. 92, pages 92-8 (1959).

Hofmann: Imidazole and its Derivatives Part I (vol. 6 The Chemistry ofHeterocyclic Compounds), pages 13- 15, New York, Interscience, 1953.

International Union of Pure and Applied Chemistry Jour. Amer. Chem. Soc.vol. 82, pages 5545-51 (1960).

Tolkmith et al.: Science vol. 158, pages 1462-3 (1967).

NATALIE TROUSOF, Primary Examiner US. Cl. X.R.

